JPH03264509A - Pasty composition of catalyst for dental adhesive - Google Patents

Abstract

PURPOSE:To obtain the subject composition, having high catalytic activity and capable of improving adhesion of dental resins to tooth dentines by mixing tri-n-borane and/or a partial oxide thereof with specific particles in an inert atmosphere. CONSTITUTION:A composition obtained by mixing (A) 50-80 pts.wt., especially 55-75 pts.wt. tri-n-butylborane(TBB) and/or partial oxide of the TBB prepared by reacting <=0.2mol, especially <=0.1mol oxygen with 1mol TBB with (B) 20-50 pts. wt., especially 25-45 pts.wt. particles containing >=20wt.%, especially >=25wt.% acrylic acid ester polymer (having 1-100mum, especially 4-20mum particle diameter) with the average particle diameter within the range of 7-20mum in an inert atmosphere. The aforementioned composition is readily preserved and handled without any danger of ignition and used in an amount of, e.g. normally 0.5-10 pts.wt. based on 100 pts.wt. methyl methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention has high catalytic activity, can improve the adhesion between resins for meat materials and tooth dentin, and can be stored without the risk of ignition. and an easy-to-handle catalyst paste composition for dental adhesives.

Technical Background of the Invention Acrylic resins such as methyl methacrylate (MMA) are widely used as dental resins used for denture base materials, dental crown feed, filling materials, orthodontic adhesives, bonding materials, etc. It is used.

The polymerization catalyst for this acrylic resin includes, for example, an ultraviolet sensitizer such as benzoyl methyl ether, a photopolymerization catalyst containing a sensitizer consisting of camphorquinone, a reducing agent, a dye, etc., and a photopolymerization catalyst containing benzoyl peroxide. Room temperature polymerization catalysts such as amine catalysts and sulfonic acids are known.

These polymerization catalysts have a high polymerization activity, and have the advantage that when added at a ratio of 1% by weight or less to the monomer, polymerization can proceed rapidly.

However, these polymerization catalysts do not contribute in any way to improving the adhesive strength between dental resin and tooth dentin.

On the other hand, as an alkyl boron polymerization initiator,
-Butylborane (hereinafter sometimes abbreviated as T or BB) is known and is used as a room-temperature polymerization initiator for dental adhesive resins whose main component is methyl methacrylate monomer.

When this dental adhesive containing TBB is applied to the tooth structure, compounds containing active hydrogen such as water and alcohol are absorbed by TBB.
Since TBB acts as a co-catalyst for B and polymerization and hardening of TBB starts from the wet surface, there is an advantage that the tooth substance and TBB have good adhesion.

Furthermore, since TBB graft polymerizes with dentin collagen, it is one of the substances that exhibits the most excellent adhesion to dentin.

Furthermore, TBB, which is contained in a resin cured product by several percent, is ultimately decomposed into n-butanol and boric acid when it reacts with water, so it is harmful to the dental pulp (probability of having an adverse effect on the dental pulp). In addition, there is less discoloration of the cured resin over time than when other polymerization initiators are used.

As described above, TBB has excellent properties as a polymerization initiator for dental adhesive resins.

However, since TBB is extremely active and difficult to handle, it is practically used as a partial oxide (hereinafter sometimes abbreviated as rT B B OJ) obtained by partially oxidizing TBB in airtight cylinders. It is sealed inside and used by taking out a few drops at a time.

However, this TBBO has a low catalytic activity, and it is usually necessary to add 6 to 7% to the monomer1, and it is also necessary to add a polymer to promote polymerization, which may lead to a decrease in the strength of the resin. It has drawbacks such as poor operability due to increased viscosity of the polymer.

A possible solution to these drawbacks is to lower the oxidation degree of T'BB, but lowering the oxidation degree of TBB causes a new problem in that TBB becomes more likely to catch fire.

Therefore, it is necessary for this TBB catalyst to maintain high catalytic activity, eliminate the risk of ignition, and further facilitate storage and handling.

Purpose of the Invention The present invention aims to solve the above-mentioned problems associated with conventional contact, and aims to improve the adhesive strength of dental resin to the dentin of teeth with high catalytic activity. It is an object of the present invention to provide a catalyst paste composition for a dental adhesive that can be easily stored and handled without the risk of ignition.

Summary of the Invention The catalyst paste I composition for dental adhesives according to the present invention comprises:
tri-n-butylborane and/or the tri-n-
50 to 80 parts by weight of the partial oxide of tri-n-butylborane obtained by reacting 0.2 mole or less of oxygen to 1 mole of butylborane, and an average particle size of 7 to 20 μin.
20 to 50 parts by weight of particles containing 20% by weight or more of an acrylic ester polymer falling within the range of 20 to 50 parts by weight are mixed in an inert atmosphere.

The catalyst paste composition for dental adhesives according to the present invention is made by mixing tri-n-butylborane or its partial oxide and specific particles in a specific ratio in an inert atmosphere. The inherently high catalytic activity of n-butylborane does not decrease, and it is possible to improve the adhesion between dental resin and tooth dentin, and it is easy to store and handle without the risk of ignition. It's easy.

DETAILED DESCRIPTION OF THE INVENTION The catalyst paste composition for dental adhesives according to the present invention will be specifically described below.

The catalyst paste composition for dental adhesives according to the present invention contains tri-n-butylborane and/or its specific partial oxide (hereinafter both may be collectively referred to as component A) from 50 to
80 parts by weight, and 20 to 50 parts by weight of particles containing 20% by weight or more of an acrylic ester polymer having an average particle diameter in the range of 7 to 20Iim (hereinafter sometimes referred to as component B). There is.

As the tri-n-butylborane used in the present invention,
It may be obtained according to a conventional method using n-butanol and boric acid, or it may be a commercially available product. In particular, it is preferable that it be sufficiently purified.

Further, the partial oxide of tri-n-butylborane used in the present invention is 0.3 mol or less, preferably 0.62 mol or less, particularly preferably 0.1 mol or less, per 1 mol of tri-n-butylborane. It is obtained by reacting oxygen.

In the present invention, tri-n-butylborane and the above-mentioned partial oxides may be used alone or in combination.

In the present invention, when using a partial oxide of tri-n-butylborane obtained by reacting 0.2 mol or less of oxygen with 1 mol of tri-n-butylborane among the components A, A catalyst paste composition for dental adhesives that maintains high catalytic activity, has no risk of ignition, and is easy to store and handle.

The paste composition for Yamashina adhesive according to the present invention is the above-mentioned A
Together with the components, it contains particles (component B) containing 20% by weight or more of an acrylic ester polymer having an average particle diameter in the range of 7 to 20 μm.

The paste-like composition for dental adhesives according to the present invention includes the above-mentioned B.
Because it contains the following components, there is no particular decrease in catalytic activity, and it is easy to store and handle.

Examples of acrylic ester polymers include polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polybutyl methacrylate, polyisobutyl methacrylate, polyt-butyl methacrylate, polyisodecyl methacrylate, and polymethacrylate. Examples include lauryl, polytridecyl methacrylate, polystearyl methacrylate, poly 2-ethylhexyl methacrylate, poly octyl methacrylate, polycyclohexyl methacrylate, and polybenzyl methacrylate.

These acrylic ester polymers may be used alone or in combination of two or more. Moreover, it is preferable to use such an acrylic ester polymer in the form of powder.

The average particle diameter of the acrylic ester polymer used in the present invention is 1 to 100 μm, preferably 3 to 50 μm, particularly preferably 4 to 20 μm.

In the present invention, among the above acrylic ester polymers, if one with an average particle diameter of 100 μm or more is used, the dissolution rate of the acrylic ester will be slow and the thickness of the adhesive layer (cement thickness in dentistry) will be large. This results in a poor fit of the prosthesis.

Component B is the above acrylic ester polymer (hereinafter referred to as B1
In addition to other ingredients (hereinafter referred to as B2
(sometimes referred to as ingredients).

This B2 component has a particle size of, for example, 20μ or less (a particle size of 20μ or more is not preferable because of the thickness of the cement, as is the case with acrylic acid ester polymers).
fine inorganic powders, such as crushed glass powder, colloidal silica, etc., fine polymer powders other than acrylic acid esters, such as polystyrene powder, polyethylene powder, etc., of 20 μm or less, and oligomer fine powders of 20 μm or less, i.e.,
Examples include 6-ura resin pulverized products and natural resin pulverized products such as rosin.

These B2 components may be used alone, or
Two or more types may be used in combination.

In the present invention, component B includes the above-mentioned B (component 10% by weight or more, preferably 20% by weight or more, particularly preferably 2% by weight or more).
It contains 5% by weight or more.

In the present invention, particularly high catalytic activity can be maintained when a component B containing 25% by weight or more of component B1 per mole of tri-n-butylborane is used. In addition, it is possible to create a catalyst paste-like composite for dental adhesives that is easy to store and handle without the risk of ignition.

In the catalyst paste composition for dental adhesives according to the present invention, the content ratio of component A and component B is 60 to 90 parts by weight, preferably 50 to 80 parts by weight, particularly preferably 55 to 80 parts by weight. 75 parts by weight, and the B component is 10 to 4
0 parts by weight, preferably 20 to 50 parts by weight, particularly preferably 25 to 45 parts by weight.

By setting the content ratio of the above-mentioned A component to 50 to 80 parts by weight, and setting the content ratio of the above-mentioned B component to 20 to 50 parts by weight, particularly high catalytic activity can be maintained and the resin for dental adhesives can be used. It is possible to improve the adhesion to the dentin of teeth, and there is no risk of ignition, and it is possible to make a catalyst paste composition for dental adhesives that is easy to store and handle.

Note that the above-mentioned A component and the above-mentioned B component are usually mixed in the presence of an inert gas such as nitrogen gas, helium gas, or argon gas, that is, in an inert atmosphere.

Resins for dental adhesives that can be polymerized and cured using the catalyst paste composition for dental adhesives according to the present invention include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and isobutyl methacrylate. , t-butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, lauryl-tridecyl methacrylate, I-lysocil methacrylate, cetyl-stearyl methacrylate, stearyl methacrylate,
Examples include acrylic resins such as 2-ethylhexyl methacrylate, 1-ctyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate.

Among these, methyl methacrylate (MMA) is particularly preferred.

The catalyst paste composition for dental adhesives according to the present invention is usually used in an amount of 0.5 to 10 parts by weight, for example, based on 100 parts by weight of the above-mentioned methyl methacrylate (MMA). In any case, the catalyst paste composition for dental adhesives according to the present invention may be used in an amount sufficient to cause the polymerization reaction of the resin for dental adhesives.

Effects of the Invention The catalyst paste composition for dental adhesives of the present invention
Partial oxide 5 of the tri-n-butylborane obtained by reacting 0.2 mol or less of oxygen with 1 mol of n-butylborane and/or the tri-n-butylborane
0 to 80 parts by weight and 20 to 50 parts by weight of particles containing 20 to 50 parts by weight of an acrylic ester polymer having an average particle diameter of 7 to 20 μm under an inert atmosphere. Therefore, it has high catalytic activity and can improve the adhesion between the resin for dental adhesives and the dentin of teeth, and does not cause a decrease in the mechanical strength of the resin for dental adhesives. Moreover, there is no danger of ignition, and it is easy to store and handle.

Furthermore, since there is no need to add a polymer to promote polymerization, operability does not deteriorate due to increased viscosity of the polymer.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Example 1 Tri-n-butylborane (TBB) was deposited on a 10 cm square glass plate under an N2 atmosphere in a dry box.

0.67 g of polyethyl methacrylate powder (manufactured by Shin Nakamura Chemical Co., Ltd., "Hybar D")
A catalyst paste composition for a dental adhesive according to the present invention was prepared by adding 1,00 J) 0,33 g and mixing using a spatula.

Regarding the obtained catalyst paste composition for granite adhesives, the flammability in the atmosphere alone, the polymerizability when mixed with methyl methacrylate (MMA), and the adhesive strength to natural teeth were evaluated. evaluated.

The results are shown in Table 1.

Note that each item was evaluated as follows.

Ignitability: One drop was placed on an acrylic plate, and the presence or absence of ignition was judged.

Polymerizability: 0.05 g of the resulting dental adhesive catalyst paste composite was added to 0.5 g of methyl methacrylate (MMA), and the polymerizability was evaluated.

Adhesive strength to natural teeth, for dental adhesives obtained by replacing TBB partial oxide in dental adhesive resin (manufactured by Sun Medical Co., Ltd., "Orthomite Super Bond") using TBB partial oxide as a polymerization catalyst The adhesive strength of a dental adhesive resin polymerized using a catalyst paste composition to natural teeth was measured.

Example 2 4 In Example 1, the amount of TBB used was changed from 0.67g to 0.
．． In addition to changing to 72g, polyethyl methacrylate-1
- The same procedure as in Example 1 was carried out except that the amount of powder used was changed from 0.33 g to 0.28 g.

The results are shown in Table 1.

Example 3 788,650 g of 788,650 g was charged into a 1 ρ eggplant-shaped flask under a N2 stream, and 16.0 g of air was added while continuously cooling and stirring 1'l' L. Q was introduced and gradually reacted to form 788 partial oxide.

Thereafter, 0.67 g of this 788 partial oxide and 0.33 g of polyethyl methacrylate 1 powder were mixed in the same manner as in Example 1 to obtain a catalyst paste composition for dental adhesives according to the present invention. was prepared and carried out in the same manner as in Example].

The results are shown in Table 1.

Comparative Example I Regarding the 788 partial oxide obtained by charging 788,650 g into an ID eggplant-shaped flask under a N2 gas flow, and gradually reacting by introducing 22.17 g of air while continuously cooling and stirring, Evaluation was performed in the same manner as in Example].

The results are shown in Table 1.

Comparative Example 2 Tri-n-butylborane (TBB, manufactured by ITJ Hon-Alkyl Aluminum Co., Ltd.) was evaluated in the same manner as in Example].

The results are shown in Table 1.

] 6 From Table 1, the catalytic paste composition for dental adhesives according to the present invention has high catalytic activity, excellent adhesive strength between the resin for dental adhesives and the dentin of teeth, and has no risk of ignition. It was confirmed that there is no gender.

Claims (1)

[Claims] (1) Tri-n-butylborane and/or 50 to 80 parts by weight of the partial oxide of tri-n-butylborane obtained by reacting 0.2 mol or less of oxygen to 1 mol of the tri-n-butylborane. and the average particle size is 7 to 20
A catalyst paste-like composition for a dental adhesive, characterized in that it is made by mixing in an inert atmosphere 20 to 50 parts by weight of particles containing 20% by weight or more of an acrylic ester polymer having a particle size in the μm range.